CN111175168A - Method for detecting content of silicon dioxide in silicon-based negative electrode material - Google Patents
Method for detecting content of silicon dioxide in silicon-based negative electrode material Download PDFInfo
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- CN111175168A CN111175168A CN202010107380.4A CN202010107380A CN111175168A CN 111175168 A CN111175168 A CN 111175168A CN 202010107380 A CN202010107380 A CN 202010107380A CN 111175168 A CN111175168 A CN 111175168A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention provides a method for detecting the content of silicon dioxide in a silicon-based negative electrode material. The method comprises the following steps: wrapping the dried silicon-based negative electrode material in a tin bag, and then packaging in a nickel bag; placing the nickel capsule in an oxygen-nitrogen analyzer, heating and melting in a graphite crucible to release oxygen element in silicon dioxide, and reacting with carbon element in the graphite crucible to generate CO and/or CO2(ii) a Determination of CO and/or CO2And converting the oxygen content into the content of silicon dioxide, thereby obtaining the content of silicon dioxide in the silicon-based negative electrode material. The method is simple and convenient to operate, rapid in detection, high in accuracy of the test result and good in repeatability.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a method for detecting the content of silicon dioxide in a silicon-based negative electrode material.
Background
As a novel energy source, the lithium ion battery has the characteristics of good cycle performance, high capacity, cleanness, environmental protection and the like, and is widely applied to a plurality of fields. In recent years, silicon-based negative electrode materials have been widely researched by many researchers in the industry due to the characteristic of extremely high specific capacity as negative electrode materials of lithium ion batteries. At present, silicon-based negative electrode materials are in a key period from a laboratory to commercial production, the content of silicon dioxide has an important influence on the capacity of the silicon-based negative electrode materials, and no method for accurately measuring the content exists in the industry at present. The methods for testing silica in other industries are mainly gravimetric and spectrophotometric.
In general, the gravimetric method is to convert silicon in a sample into silicate precipitates by using hydrofluoric acid or alkali, burn the silicate precipitates at a high temperature to form silicon dioxide, and calculate the mass change of the silicon dioxide to detect the content of the silicon dioxide in the sample. However, the silicon element and the silicon dioxide exist in the silicon-based negative electrode material at the same time, and the method can only measure the content of the silicon element, so that the content of the silicon dioxide is difficult to accurately obtain.
The spectrophotometry also changes silicon in a sample into silicon dioxide, and the content of the silicon dioxide in the silicon-based negative electrode material is difficult to measure. For example, CN106896103A discloses SiO in silicon-carbon composite material for lithium ion battery2The method comprises the steps of reacting nitric acid/hydrochloric acid and hydrofluoric acid with a sample, then developing the color of the treated sample through ammonium molybdate and a reducing agent (one or more of oxalic acid, ascorbic acid or formic acid), and then measuring the content of silicon dioxide by adopting a spectrophotometry. However, the method has many operation steps and is relatively complicated.
In summary, the existing method for detecting the content of silica in the silicon-based negative electrode material still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a method for detecting the content of silicon dioxide in a silicon-based negative electrode material. The method is simple and convenient to operate, rapid in detection, high in accuracy of the test result and good in repeatability.
In one aspect of the invention, the invention provides a method for detecting the content of silicon dioxide in a silicon-based negative electrode material. According to an embodiment of the invention, the method comprises:
wrapping the dried silicon-based negative electrode material in a tin bag, and then packaging in a nickel bag;
placing the nickel capsule in an oxygen-nitrogen analyzer, heating and melting in a graphite crucible to release oxygen element in silicon dioxide, and reacting with carbon element in the graphite crucible to generate CO and/or CO2；
Determination of CO and/or CO2And converting the oxygen content into the content of silicon dioxide, thereby obtaining the content of silicon dioxide in the silicon-based negative electrode material.
By using the method for detecting the content of silicon dioxide in the silicon-based negative electrode material, provided by the embodiment of the invention, before testing, the moisture in the material is removed by drying the silicon-based negative electrode material sample, and the interference of the moisture on the determination of the oxygen content is discharged; the nested form of the tin bag and the nickel bag is adopted to package the silicon-based negative electrode material powder, so that the sample is heated more uniformly, the silicon-based negative electrode material can be promoted to be melted, and the release of oxygen elements in silicon dioxide is facilitated. Because only silicon dioxide is a substance containing oxygen element in the silicon-based negative electrode material, the content of the silicon dioxide in the silicon-based negative electrode material is calculated by measuring the content of the oxygen element in the silicon-based negative electrode material. The detection method solves the problem that in the prior art, all silicon elements in a sample are extracted by adopting hydrofluoric acid or alkali in a gravimetric method and a spectrophotometric method, and only silicon dioxide cannot be extracted, and realizes simple, rapid and accurate test of the content of the silicon dioxide in the silicon-based negative electrode material.
In addition, the method for detecting the content of silica in the silicon-based anode material provided by the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the invention, the drying operation comprises: drying the silicon-based negative electrode material for 1.5-3h at 40-60 ℃ in a vacuum drying oven with the vacuum degree of less than or equal to 133 Pa.
During drying, proper temperature and time are controlled to remove moisture interference and prevent material oxidation.
Examples of the drying temperature include: 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃.
Examples of the drying time include: 1.5h, 2h and 3 h.
In some embodiments, the silicon-based anode material is dried for 2 hours at 50 ℃ in a vacuum drying oven with the vacuum degree of less than or equal to 133 Pa.
According to some embodiments of the invention, the heating power of the oxynitrimeter is 3.5-6.5kW, for example: 3.5kW, 4kW, 4.5kW, 5kW, 5.5kW, 6kW, 6.5 kW. The lower heating power cannot completely melt the silica and cannot sufficiently release the oxygen element.
Particularly preferably, the heating power of the oxygen-nitrogen analyzer is 5.5 kW.
Furthermore, generally, the oxygen and nitrogen analyzer requires standardized calibration before use. Selecting an analysis channel according to the type and the content of the sample, analyzing by using the selected standard sample, and performing single-point standardized correction according to the operation procedure of the instrument when the third analysis value does not exceed the allowable difference of the standard substance; and analyzing the selected standard sample, wherein the analysis value is within the allowable difference range, the sample analysis can be carried out, and otherwise, the standardization correction is carried out again.
The silicon-based negative electrode material refers to a silicon-carbon negative electrode material or a silicon-oxygen negative electrode material and the like.
The invention has the following technical effects:
the detection method solves the problem that in the prior art, all silicon elements in a sample are extracted by adopting hydrofluoric acid or alkali in a gravimetric method and a spectrophotometric method, and only silicon dioxide cannot be extracted, and realizes simple, rapid and accurate test of the content of the silicon dioxide in the silicon-based negative electrode material.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Drying the silicon-based negative electrode material in a vacuum drying oven (the vacuum degree is less than or equal to 133Pa) at 50 ℃ for 2 hours, and transferring the silicon-based negative electrode material into a dryer for temporary storage; taking about 0.05g of silicon-based negative electrode material, precisely weighing, wrapping in a tin bag, packaging in a nickel bag, putting into a feed inlet of an oxygen-nitrogen analyzer, selecting a common graphite crucible as a heating container, setting the heating power to be 5.5kW, directly obtaining an oxygen content test value of silicon dioxide in the silicon-based negative electrode material within about 3 minutes, repeatedly testing for 3 times in parallel to obtain a relatively consistent reading, retaining 2 effective digits after a decimal point, taking an average value W (O) of the average value, and obtaining the content W (SiO) of the silicon dioxide by conversion2) W (O)/53.26%, wherein 53.26% is the specific gravity of the oxygen element in the silica. The analytical test results are shown in tables 1 and 2.
Example 2
Drying the silicon-based negative electrode material in a vacuum drying oven (the vacuum degree is less than or equal to 133Pa) at 50 ℃ for 2 hours, and transferring the silicon-based negative electrode material into a dryer for temporary storage; taking about 0.05g of silicon-based negative electrode material, precisely weighing, wrapping in a tin bag, packaging in a nickel bag, putting into a feed inlet of an oxygen-nitrogen analyzer, selecting a common graphite crucible as a heating container, setting the heating power to be 5.0kW, directly obtaining an oxygen content test value of silicon dioxide in the silicon-based negative electrode material within about 3 minutes, repeatedly testing for 3 times in parallel to obtain a relatively consistent reading, retaining 2 effective digits after a decimal point, taking an average value W (O) of the average value, and obtaining the content W (SiO) of the silicon dioxide by conversion2) W (O)/53.26%, wherein 53.26% is the specific gravity of the oxygen element in the silica. The analytical test results are shown in tables 1 and 2.
Comparative example 1
Drying the silicon-based negative electrode material in a vacuum drying oven (the vacuum degree is less than or equal to 133Pa) at 50 ℃ for 2 hours, and transferring the silicon-based negative electrode material into a dryer for temporary storage; taking about 0.05g of silicon-based anode material, precisely weighing, wrapping in tin bag, feeding into feed inlet of oxygen-nitrogen analyzer, and selecting common graphite crucibleHeating power is set to be 5.5kW for heating a container, a test value of the oxygen content of silicon dioxide in the silicon-based anode material can be directly obtained within about 3 minutes, parallel repeated tests are carried out for 3 times to obtain a relatively consistent reading, 2 significant digits after decimal point are reserved, an average value W (O) of the obtained values is taken, and the content W (SiO) of the silicon dioxide is obtained through conversion2) W (O)/53.26%, wherein 53.26% is the specific gravity of the oxygen element in the silica. The analytical test results are shown in tables 1 and 2.
Comparative example 2
Drying the silicon-based negative electrode material in a vacuum drying oven (the vacuum degree is less than or equal to 133Pa) at 50 ℃ for 2 hours, and transferring the silicon-based negative electrode material into a dryer for temporary storage; taking about 0.05g of silicon-based negative electrode material, precisely weighing, packaging in a nickel bag, putting into a feed inlet of an oxygen-nitrogen analyzer, selecting a common graphite crucible as a heating container, setting the heating power to be 5.5kW, directly obtaining the oxygen content test value of silicon dioxide in the silicon-based negative electrode material in about 3 minutes, repeatedly testing for 3 times in parallel to obtain a relatively consistent reading, retaining 2 effective digits after a decimal point, taking an average value W (O) of the effective digits, and obtaining the content W (SiO) of the silicon dioxide by conversion2) W (O)/53.26%, wherein 53.26% is the specific gravity of the oxygen element in the silica. The analytical test results are shown in tables 1 and 2.
Comparative example 3
The silicon-based negative electrode material is not dried, about 0.05g of the silicon-based negative electrode material is taken, precisely weighed, wrapped in a tin bag and then packaged in a nickel bag, a feed inlet of an oxygen-nitrogen analyzer is put into the tin bag, a common graphite crucible is selected as a heating container, the heating power is set to be 5.5kW, the oxygen content test value of silicon dioxide in the silicon-based negative electrode material can be directly obtained about 3 minutes, parallel repeated testing is carried out for 3 times to obtain a more consistent reading, 2 effective digits after decimal point are reserved, the average value W (O) is taken, and the content W (SiO) of the silicon dioxide is obtained by conversion2) W (O)/53.26%, wherein 53.26% is the specific gravity of the oxygen element in the silica. The analytical test results are shown in tables 1 and 2.
TABLE 1 elemental oxygen content
TABLE 2 silicon dioxide content in silicon-based anode materials
As can be seen from the results in tables 1 and 2, in the example 1, the sample is uniformly heated in the melting process by adopting the mode of coating the nickel capsule with the tin capsule, the oxygen element in the silicon dioxide in the sample is completely released, and the test result is stable; in example 2, the heating power was reduced, and the release of oxygen element was incomplete, resulting in a lower test result. Compared with the example 1, in the comparative example 1, the sample is wrapped by the tin bag, silicon dioxide cannot be well melted, so that oxygen is incompletely released, and the test result is low; in the comparative example 2, only the nickel capsule is used for packaging the sample, and the silicon dioxide can not be well melted, so that the oxygen element is not completely released, and the test result is low; in comparative example 3, the same procedure as in example 1 was conducted except that the sample was not dried, and from the comparison of the results, it can be seen that the result of comparative example 3 in which the drying treatment was not conducted was significantly higher than that of example 1, and it is considered that the higher oxygen content was derived from the moisture in the sample.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (5)
1. A method for detecting the content of silicon dioxide in a silicon-based negative electrode material is characterized by comprising the following steps:
drying the silicon-based negative electrode material;
wrapping the dried silicon-based negative electrode material in a tin bag, and then packaging in a nickel bag;
placing the nickel capsule in an oxygen-nitrogen analyzer, heating and melting in a graphite crucible to release oxygen element in silicon dioxide, and reacting with carbon element in a graphite dry pot to generate CO and/or CO2；
Determination of CO and/or CO2And converting the oxygen content into the content of silicon dioxide, thereby obtaining the content of silicon dioxide in the silicon-based negative electrode material.
2. The method for detecting the content of silicon dioxide in the silicon-based anode material as claimed in claim 1, wherein the drying operation comprises: drying the silicon-based negative electrode material for 1.5-3h at 40-60 ℃ in a vacuum drying oven with the vacuum degree of less than or equal to 133 Pa.
3. The method for detecting the content of silicon dioxide in the silicon-based anode material as claimed in claim 1, wherein the heating power of the oxygen-nitrogen analyzer is 3.5-6.5 kW.
4. The method for detecting the content of silicon dioxide in the silicon-based anode material as claimed in claim 3, wherein the heating power of the oxygen-nitrogen analyzer is 5.5 kW.
5. The method for detecting the content of silicon dioxide in the silicon-based anode material according to any one of claims 1 to 4, wherein the silicon-based anode material is a silicon-carbon anode material or a silicon-oxygen anode material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023184611A1 (en) * | 2022-03-29 | 2023-10-05 | 安徽理工大学 | System and method for detecting concentration of free silicon dioxide in coal dust |
| US11940376B2 (en) | 2022-03-29 | 2024-03-26 | Anhui University of Science and Technology | System and method for detecting concentration of free SiO2 in coal dust |
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| CN107064045A (en) * | 2016-12-12 | 2017-08-18 | 中核北方核燃料元件有限公司 | The assay method of oxygen content in a kind of composite material of silicon carbide |
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| CN103528912A (en) * | 2013-09-18 | 2014-01-22 | 刘俊菊 | Rapid system analysis for limestone and dolomite |
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Application publication date: 20200519 |